Thermodynamic Feedback Mechanisms for Mitigating Polarization in Lithium‐Ion Batteries

Abstract The performance of lithium‐ion batteries (LIBs) is intrinsically determined by the interplay between the kinetic and thermodynamic processes, which jointly govern the polarization dynamics across multiple scales. Extensive efforts have been directed toward alleviating kinetic limitations, but the essential role of thermodynamic factors, particularly under extreme operating conditions, has been largely overlooked. This oversight has impeded the development of comprehensive design principle for optimizing LIBs. In this study, we systematically investigate the coupled effects between thermodynamics and kinetics using advanced multiphysics simulations. We identify the slope of the equilibrium potential profile as a pivotal thermodynamic parameter. Steeper slopes have been demonstrated to induce stronger negative feedback, thereby effectively mitigating polarization heterogeneity and realizing the consistent electrode utilization. Based on this insight, we propose a design strategy centered on steepening the equilibrium potential to enhance thermodynamic feedback. This approach achieves a remarkable 80% reduction in polarization heterogeneity, significantly improving operational stability. Our work establishes a theoretical framework for polarization dynamics and offers actionable thermodynamic design principles, paves the way for the development of LIBs capable of extreme operating conditions.